CN107298738B - A kind of low temperature resistant unsaturated polyester resin compositions and preparation method thereof - Google Patents
A kind of low temperature resistant unsaturated polyester resin compositions and preparation method thereof Download PDFInfo
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- CN107298738B CN107298738B CN201710533220.4A CN201710533220A CN107298738B CN 107298738 B CN107298738 B CN 107298738B CN 201710533220 A CN201710533220 A CN 201710533220A CN 107298738 B CN107298738 B CN 107298738B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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Abstract
A kind of low temperature resistant unsaturated polyester resin compositions, in parts by weight, it includes: 46-52 parts of maleic anhydride, 112-128 parts of straight chained alkyl glycol, 29-38 parts of M-phthalic acid, 22-29 parts of itaconic acid, 1 that it, which prepares raw material, 6-8 parts of 2- propylene glycol, 33-42 parts of triethylene glycol, 30-38 parts of 3,4- thiophene dicarboxylic acid, 46-57 parts of styrene, 19-25 parts of 2- vinyl thiophene.
Description
Technical field
The present invention relates to the field of polymers, and in particular to a kind of low temperature resistant unsaturated polyester resin compositions and its preparation side
Method.
Background technique
In recent years, with the fast development of science and technology, the gradually decreasing of synthesis cost, the raising of quality of materials, synthesis
Resin becomes one of demand and the maximum material of yield in the world.The application field of synthetic resin is constantly widened, and in agricultural, is built
It builds, there is important role in the fields such as automobile and electronics.Unsaturated polyester resin is industry important in Resin Industry, has matter
Amount is light, high-intensitive, and excellent performances such as workability etc. easily are used to prepare the product of various large scale structure complexity, are that one kind has very
The versatile material of big superiority.Domestic at present is in the state that need to be greater than confession, insatiable hunger for the demand of unsaturated polyester resin
Production and processing industry with polyester grow up therewith.In countries such as Japan, North Americas, unsaturated polyester resin industrial development is fast
Speed, and have huge market.
Unsaturated polyester resin (UPR) is by saturation dihydric alcohol and unsaturated dibasic acid, unsaturated dicarboxylic acid anhydride dehydration contracting
Fluoropolymer resin made of conjunction.Long chain is presented in usual resinous molecular structure, and structure has the insatiable hunger of special non-aromatic containing in
And carbon-carbon double bond, the thermosetting plastics of crosslinking net macromolecular structure is reacted under crosslinking agent and initiator effect.Polymerization
The property of object is determined by the type of used monomer and the chain structure of formation.
The synthesis material of unsaturated polyester (UP) includes unsaturated dibasic acid class and alcohols.Contain unsaturation in unsaturated dibasic acid
Carbon-carbon double bond.In unsaturated polyester (UP) preparation process, the unsaturated dibasic acid for participating in reaction can introduce unsaturated carbon for resin
Carbon double bond.The proportion of unsaturated dibasic acid is higher, and the content of the unsaturated double-bond contained in molecule will be higher, crosslinking degree
Will be higher, because the heat distortion temperature of resin will be higher after solidification.And the structure of binary acid also can generate one to polymer
Fixed influence.
It is reacted in the form of acid anhydrides with alcohol in maleic anhydride molecular structure, more other binary acid were reacting
A molecular water is generated in journey less.But maleic anhydride is easy to produce isomerization, finally obtained tree during reacting with alcohol
Resin difference prepared by the structure and fumaric acid of rouge is simultaneously little.
Fumaric acid acid anhydride, be otherwise known as fumaric acid anhydride, is the transisomer of maleic anhydride.Transconfiguration is easy molecule
Between more well-regulated arrangement.Due to being the resin of Material synthesis than Resin crystallization prepared by maleic acid using fumaric acid
Property is stronger, softening point is higher.It is more more stable than cis- maleic anhydride, and fusing point is higher.
Alcohols reacts to form long-chain polymer with unsaturated dibasic acid.Usually using the alcohols energy of molecular chain length or line style
Improve the flexibility of polymer.The alcohols being commonly used has ethylene glycol, diethylene glycol, 1,2- propylene glycol, neopentyl glycol, a contracting diethyl
Two pure and mild polyalcohols etc..
Ethylene glycol is simplest one kind of structure in di-alcohols.Ethylene glycol is due to having symmetry in structure, so that poly-
Resin made of conjunction has preferable crystallinity.The unsaturated polyester (UP) that fumaric acid and ethylene glycol synthesize is exactly a kind of easily precipitation
The resin of crystal.And the intermiscibility between ethylene glycol and styrene is poor, is often used in mixed way with other alcohols.
Diethylene glycol can effectively improve the mechanical property of product.If as having aromatic ring structure in alcohol, so that it may be made rigid
The polymer of property structure, and the water imbibition of product can be effectively reduced.
1,2-PD has stronger activity, can be with many binary acid reactive polymerics at resin.Simultaneously because price
Cheap, 1,2-PD is a kind of more common dihydric alcohol.
Neopentyl glycol molecular structure is a kind of linear structure, has good symmetry.Since it is with symmetrical structure, newly
Pentanediol has preferable crystallinity.Neopentyl glycol, which reacts the resin generated with fumaric acid, has crystallinity.And the alcohol is advantageous
In the alkali resistance and water resistance that improve synthetic resin, it is not easy that hydrolysis occurs with hydrone.But neopentyl glycol and styrene
Poor compatibility, need to be used in mixed way with other alcohols in use.
The linear structure of diglycol molecular structure, and strand is longer in small molecular alcohol.It is prepared as raw material
Unsaturated polyester resin have preferable flexible, can reduce the crystallinity of resin.But since there are more in the resin
Oxygen bridge, resin have stronger sensibility to water.Compatibility between this alcohol and styrene is not so good as propylene glycol.
Polyalcohol is exactly in molecule containing the alcohol micromolecular for having more than 2 hydroxy functional groups.When using this alcohols as raw material
It is easy to produce branch, forms reticular structure.Therefore the mechanical property of this resin is good.But due to being easy to produce in the course of the polymerization process
Raw branch, leads to molecule winding between prepolymer and viscosity increases, premature gelation, is difficult to control reaction process.
Unsaturated polyester (UP) have good mechanical property, electrical property and chemical-resistance, and raw material be easy to get it is low with price
Honest and clean, composite material is widely used in the industry such as ship, automobile, building materials industry.But generally there are poor toughness, strong for the solidfied material of UPR
Spend it is not high, be easy cracking, the disadvantages of shrinking percentage is big, to limit its scope of application.
Summary of the invention
In order to solve prior art problem, the first aspect of the present invention provides a kind of low temperature resistant unsaturated polyester resin combination
Object, in parts by weight, preparing raw material includes: 46-52 parts of maleic anhydride, 112-128 parts of straight chained alkyl glycol, M-phthalic acid
29-38 parts, 22-29 parts of itaconic acid, 6-8 parts of 1,2- propylene glycol, 33-42 parts of triethylene glycol, 30-38 parts of 3,4- thiophene dicarboxylic acid, benzene
46-57 parts of ethylene, 19-25 parts of 2- vinyl thiophene.
In some embodiments, low temperature resistant unsaturated polyester resin compositions as described above, in parts by weight, system
Standby raw material includes: 49 parts of maleic anhydride, 120 parts of straight chained alkyl glycol, 33.2 parts of M-phthalic acid, 26 parts of itaconic acid, 1,2- third
7.6 parts of glycol, 37.5 parts of triethylene glycol, 34.4 parts of 3,4- thiophene dicarboxylic acid, 52 parts of styrene, 22 parts of 2- vinyl thiophene.
In some embodiments, the straight chained alkyl glycol contains 4-12 carbon atom.
In some embodiments, the straight chained alkyl glycol contains 8-10 carbon atom.
In some embodiments, the straight chained alkyl glycol is nonanediol.
In some embodiments, the molar ratio of the styrene and 2- vinyl thiophene is 5:2.
In some embodiments, the 2- vinyl thiophene and 3, the molar ratio of 4- thiophene dicarboxylic acid are 1:1.
The second aspect of the present invention provides a kind of preparation method of low temperature resistant unsaturated polyester resin compositions, including as follows
Step: the air in reaction kettle is excluded with High Purity Nitrogen, 1,2-PD 6-8 parts, 33-42 parts of triethylene glycol, maleic anhydride 46- is added
52 parts, 80 DEG C are warming up to, stirs 30min, is then added M-phthalic acid 29-38 parts, then be warming up to 145 DEG C, stirring 1h, then plus
Enter 112-128 parts of straight chained alkyl glycol, be warming up to 210 DEG C, stir 1h, adds 30-38 parts of 3,4- thiophene dicarboxylic acid and clothing health
It is 22-29 parts sour, 4h is stirred, is cooled to 160 DEG C, 19-25 parts of 2- vinyl thiophene is added, stirs evenly, continue to be cooled to 95 DEG C,
Be added styrene 46-57 parts, be cooled to room temperature to get.
In some embodiments, the preparation method of low temperature resistant unsaturated polyester resin compositions includes the following steps: to use
High Purity Nitrogen excludes the air in reaction kettle, and 7.6 parts of 1,2-PD, 37.5 parts of triethylene glycol, 49 parts of maleic anhydride is added, is warming up to
80 DEG C, 30min is stirred, is then added 33.2 parts of M-phthalic acid, then be warming up to 145 DEG C, 1h is stirred, adds straight chained alkyl two
120 parts of alcohol, 210 DEG C are warming up to, stirs 1h, adds 34.4 parts and 26 parts of itaconic acid of 3,4- thiophene dicarboxylic acid, stirs 4h, it is cooling
To 160 DEG C, 22 parts of 2- vinyl thiophene are added, is stirred evenly, continued to be cooled to 95 DEG C, be added 52 parts of styrene, be cooled to room
Temperature to get.
The third aspect of the present invention provides a kind of curing method of low temperature resistant unsaturated polyester resin compositions, to low temperature resistant
The organic peroxide of 0.5wt% is added in unsaturated polyester resin compositions, stirs evenly, adds 0.01wt% isooctyl acid
Cobalt forms in a mold.
The fourth aspect of the present invention provides a kind of low temperature resistant unsaturated polyester resin compositions in auto industry, aircraft system
It makes, radar manufacture, ship, the application in field of chemical equipment.
Specific embodiment
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this hair can be more easily to understand
Bright content.Unless otherwise defined, all technologies used herein and scientific term have common with fields of the present invention
The normally understood identical meaning of technical staff.When there is a conflict, the definition in this specification shall prevail.
As used herein term " by ... preparation " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover non-exclusionism includes.For example, the combination comprising listed elements
Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or
Such composition, step, method, product or the intrinsic element of device.
Conjunction " Consists of " excludes any element that do not point out, step or component.If in claim, this
Phrase will make claim closed, so that it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body,
It is only limited to element described in the clause；Other elements are not excluded except the claim as a whole.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end
Value and all integers and score in the range.
Singular includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or it is " any
It is a kind of " refer to that the item described thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used to modify quantity, and it is specific to indicate that the present invention is not limited to this
Quantity further includes the acceptable modified part without will lead to the change of dependency basis this function close with the quantity.Phase
It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, approximate
Term likely corresponds to the precision of the instrument of measurement numerical value.In present specification and claims, range limits can be with
Combination and/or exchange, these ranges if not stated otherwise include all subranges contained therebetween.
In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component
(i.e. frequency of occurrence) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number
The element or component of form also include plural form, unless the obvious purport of the quantity refers to singular.
The first aspect of the present invention provides a kind of low temperature resistant unsaturated polyester resin compositions, in parts by weight, preparation
Raw material includes: 46-52 parts of maleic anhydride, 112-128 parts of straight chained alkyl glycol, 29-38 parts of M-phthalic acid, itaconic acid 22-29
Part, 6-8 parts of 1,2- propylene glycol, 33-42 parts of triethylene glycol, 30-38 parts of 3,4- thiophene dicarboxylic acid, 46-57 parts of styrene, 2- vinyl
19-25 parts of thiophene.
In some embodiments, low temperature resistant unsaturated polyester resin compositions as described above, in parts by weight, system
Standby raw material includes: 49 parts of maleic anhydride, 120 parts of straight chained alkyl glycol, 33.2 parts of M-phthalic acid, 26 parts of itaconic acid, 1,2- third
7.6 parts of glycol, 37.5 parts of triethylene glycol, 34.4 parts of 3,4- thiophene dicarboxylic acid, 52 parts of styrene, 22 parts of 2- vinyl thiophene.
In some embodiments, the straight chained alkyl glycol contains 4-12 carbon atom.
In some embodiments, the straight chained alkyl glycol contains 8-10 carbon atom.
In some embodiments, the straight chained alkyl glycol is nonanediol.
In some embodiments, the molar ratio of the styrene and 2- vinyl thiophene is 5:2.
In some embodiments, the 2- vinyl thiophene and 3, the molar ratio of 4- thiophene dicarboxylic acid are 1:1.
Maleic anhydride, CAS accession number 108-31-6, also known as maleic anhydride (MAH), abbreviation cis-butenedioic anhydride, are maleics two
The acid anhydrides of acid, is at room temperature sour colourless or white solid, molecular formula C4H2O3.
The specific example of straight chained alkyl glycol includes, 1,4-butanediol, 1,5-PD, 1,6- hexylene glycol, 1,7- heptan two
Alcohol, 1,8- ethohexadiol, 1,9- nonanediol, 1,10- decanediol, 11 glycol of 1,11-, 12 glycol of 1,12-.
In some preferred embodiments, the straight chained alkyl glycol is 1,8- ethohexadiol, 1,9- nonanediol, 1,10-
Decanediol.
In some preferred embodiments, the straight chained alkyl glycol is 1,9- nonanediol.
1,9- nonanediol, CAS accession number 3937-56-2 are a kind of important organic diols, and a kind of purposes is wider to be had
Machine raw material is basic material in organic synthesis industry；It can also be used to produce lubricant, plasticizer simultaneously；It can also be used for medicine
Etc.；It can be used for liquid crystal material, degradable function high molecular material；Fragrance, lubricating oil, ink, coating, cosmetics, plasticising
The production of agent and various additives etc..It can also be used in the synthesis of a variety of organic intermediates.
M-phthalic acid, CAS accession number 121-91-5, also referred to as isophathalic acid, 1,3- phthalic acid.It is a kind of white crystalline
Powder or acicular crystal.It is soluble in pure and mild glacial acetic acid, be slightly soluble in boiling water but does not dissolve in cold water, is practically insoluble in benzene and petroleum ether.
Itaconic acid, CAS accession number 97-65-4, also referred to as methene succinic acid, methylene-succinic acid are that unsaturated binary is organic
Acid.It contains unsaturated double-bond, has active chemical property, can carry out the polymerization between itself, also can be with other monomers such as propylene
The polymerization such as nitrile, is dissolved in water, other solvents such as ethyl alcohol；It can be carried out various addition reactions, esterification and polymerization reaction, be chemical conjunction
At the important source material of industry and the important source material of Chemical Manufacture.
1,2-PD, CAS 57-55-6, with water, ethyl alcohol and a variety of immiscible organic solvents, chemical formula C3H8O2.
It is colourless viscous liquid under normality, it is almost tasteless, it carefully hears slightly sweet.Propylene glycol can be used as the raw material of unsaturated polyester resin.Changing
Wetting agent can be used as with glycerol or sorbierite cooperation in cosmetic, toothpaste and perfumed soap.It is used as damping, even hair agent in hair dye,
As antifreezing agent, it is also used to glassine paper, plasticizer and pharmaceuticals industry.
Triethylene glycol, CAS 112-27-6.3,4- thiophene dicarboxylic acids, CAS 4282-29-5.Styrene, CAS accession number
100-42-5.2- vinyl thiophene, CAS accession number 1918-82-7.
Inventor has found under study for action, and the toughness of unsaturated polyester resin can be adjusted using straight chained alkyl glycol, introduces
3,4- thiophene dicarboxylic acids can increase the intensity of unsaturated polyester resin, and intensity especially at low temperature also has at -20 DEG C
There is good intensity.Interaction between thiophene on sulphur is to more crosslinking points are introduced in system, but also packing of molecules
It is closer, the gap in three-dimensional netted macromolecular is smaller.2- vinyl thiophene is added to styrene according to a certain percentage
In, shrinking percentage can be adjusted while guaranteeing the low temperature intensity of resin.Expand the application range of unsaturated polyester resin.
The second aspect of the present invention provides a kind of preparation method of low temperature resistant unsaturated polyester resin compositions, including as follows
Step: the air in reaction kettle is excluded with High Purity Nitrogen, 1,2-PD 6-8 parts, 33-42 parts of triethylene glycol, maleic anhydride 46- is added
52 parts, 80 DEG C are warming up to, stirs 30min, is then added M-phthalic acid 29-38 parts, then be warming up to 145 DEG C, stirring 1h, then plus
Enter 112-128 parts of straight chained alkyl glycol, be warming up to 210 DEG C, stir 1h, adds 30-38 parts of 3,4- thiophene dicarboxylic acid and clothing health
It is 22-29 parts sour, 4h is stirred, is cooled to 160 DEG C, 19-25 parts of 2- vinyl thiophene is added, stirs evenly, continue to be cooled to 95 DEG C,
Be added styrene 46-57 parts, be cooled to room temperature to get.
In some embodiments, the preparation method of low temperature resistant unsaturated polyester resin compositions includes the following steps: to use
High Purity Nitrogen excludes the air in reaction kettle, and 7.6 parts of 1,2-PD, 37.5 parts of triethylene glycol, 49 parts of maleic anhydride is added, is warming up to
80 DEG C, 30min is stirred, is then added 33.2 parts of M-phthalic acid, then be warming up to 145 DEG C, 1h is stirred, adds straight chained alkyl two
120 parts of alcohol, 210 DEG C are warming up to, stirs 1h, adds 34.4 parts and 26 parts of itaconic acid of 3,4- thiophene dicarboxylic acid, stirs 4h, it is cooling
To 160 DEG C, 22 parts of 2- vinyl thiophene are added, is stirred evenly, continued to be cooled to 95 DEG C, be added 52 parts of styrene, be cooled to room
Temperature to get.
The acid value that existing synthetic method obtains is 20-50mg/g, and synthetic method provided by the invention can allow respectively
A component is sufficiently reacted, and the acid value of composition is 10-15mg/g.
Acid value is the milligram number of KOH required for neutralizing 1g unsaturated polyester (UP) composition.
The measuring method of acid value are as follows:
1. taking 1g phenolphthalein to mix with 99g ethyl alcohol is made into indicator；
2. toluene and ethyl alcohol is taken to be made into mixed solvent with volume ratio 1:1；
3. weighing 5.6gKOH to be dissolved in 1L distilled water, mole of 0.1g o-2 potassium acid hydrogen potassium calibration KOH solution is then taken
Indicator is added in concentration；
4. taking 1g unsaturated polyester resin compositions in 250mL conical flask, mixed solvent is taken with 20mL pipette respectively
Be added in the conical flask containing unsaturated polyester resin compositions and blank conical flask in；
5. being added separately to 3 drop indicator in the conical flask containing unsaturated polyester resin compositions and blank taper
It in bottle, is titrated with KOH solution, the volume of record consumption KOH solution, Unit/mL obtains molten containing unsaturated polyester resin compositions
Liquid and blank solution are denoted as V and V0 respectively；
6. acid value calculation formula:
M is the quality of unsaturated polyester resin compositions, g；V is KOH milligrams of numbers consumed by sample；V0 is blank sample
Consumed KOH milligrams of number；N is the molar concentration of KOH solution, mol/L.
The third aspect of the present invention provides a kind of curing method of low temperature resistant unsaturated polyester resin compositions, to low temperature resistant
The organic peroxide of 0.5wt% is added in unsaturated polyester resin compositions, stirs evenly, adds 0.01wt% isooctyl acid
Cobalt forms in a mold.
The fourth aspect of the present invention provides a kind of low temperature resistant unsaturated polyester resin compositions in auto industry, aircraft system
It makes, radar manufacture, ship, the application in field of chemical equipment.
The present invention is further explained combined with specific embodiments below.
Embodiment 1
A kind of low temperature resistant unsaturated polyester resin compositions, in parts by weight, preparing raw material includes: maleic anhydride 49
Part, 120 parts of 1,9- nonanediol, 33.2 parts of M-phthalic acid, 26 parts of itaconic acid, 7.6 parts of 1,2- propylene glycol, 37.5 parts of triethylene glycol,
34.4 parts of 3,4- thiophene dicarboxylic acid, 52 parts of styrene, 22 parts of 2- vinyl thiophene.
Preparation method: with High Purity Nitrogen exclude reaction kettle in air, be added 7.6 parts of 1,2-PD, 37.5 parts of triethylene glycol,
49 parts of maleic anhydride, 80 DEG C are warming up to, stirs 30min, is then added 33.2 parts of M-phthalic acid, then be warming up to 145 DEG C, is stirred
1h adds 120 parts of 1,9- nonanediol, is warming up to 210 DEG C, stirs 1h, adds 34.4 parts of 3,4- thiophene dicarboxylic acid and clothing health
26 parts of acid stirs 4h, is cooled to 160 DEG C, is added 22 parts of 2- vinyl thiophene, stirs evenly, and continues to be cooled to 95 DEG C, benzene is added
52 parts of ethylene, be cooled to room temperature to get.Acid value 12mg/g.
Curing method: the peroxide of the 0.5wt% of composition weight is added into low temperature resistant unsaturated polyester resin compositions
Change cyclohexanone, stirs evenly, add the 0.01wt% cobalt iso-octoate of composition weight, form in a mold.
Embodiment 2
A kind of low temperature resistant unsaturated polyester resin compositions, in parts by weight, preparing raw material includes: maleic anhydride 49
Part, 120 parts of 1,8- ethohexadiol, 33.2 parts of M-phthalic acid, 26 parts of itaconic acid, 7.6 parts of 1,2- propylene glycol, 37.5 parts of triethylene glycol,
34.4 parts of 3,4- thiophene dicarboxylic acid, 52 parts of styrene, 22 parts of 2- vinyl thiophene.
Preparation method: with High Purity Nitrogen exclude reaction kettle in air, be added 7.6 parts of 1,2-PD, 37.5 parts of triethylene glycol,
49 parts of maleic anhydride, 80 DEG C are warming up to, stirs 30min, is then added 33.2 parts of M-phthalic acid, then be warming up to 145 DEG C, is stirred
1h adds 120 parts of 1,8- ethohexadiol, is warming up to 210 DEG C, stirs 1h, adds 34.4 parts of 3,4- thiophene dicarboxylic acid and clothing health
26 parts of acid stirs 4h, is cooled to 160 DEG C, is added 22 parts of 2- vinyl thiophene, stirs evenly, and continues to be cooled to 95 DEG C, benzene is added
52 parts of ethylene, be cooled to room temperature to get.Acid value 14mg/g.
Curing method: the peroxide of the 0.5wt% of composition weight is added into low temperature resistant unsaturated polyester resin compositions
Change cyclohexanone, stirs evenly, add the 0.01wt% cobalt iso-octoate of composition weight, form in a mold.
Embodiment 3
A kind of low temperature resistant unsaturated polyester resin compositions, in parts by weight, preparing raw material includes: maleic anhydride 49
Part, 120 parts of 1,10- decanediol, 33.2 parts of M-phthalic acid, 26 parts of itaconic acid, 7.6 parts of 1,2- propylene glycol, 37.5 parts of triethylene glycol,
34.4 parts of 3,4- thiophene dicarboxylic acid, 52 parts of styrene, 22 parts of 2- vinyl thiophene.
Preparation method: with High Purity Nitrogen exclude reaction kettle in air, be added 7.6 parts of 1,2-PD, 37.5 parts of triethylene glycol,
49 parts of maleic anhydride, 80 DEG C are warming up to, stirs 30min, is then added 33.2 parts of M-phthalic acid, then be warming up to 145 DEG C, is stirred
1h adds 120 parts of 1,10- decanediol, is warming up to 210 DEG C, stirs 1h, adds 34.4 parts of 3,4- thiophene dicarboxylic acid and clothing health
26 parts of acid stirs 4h, is cooled to 160 DEG C, is added 22 parts of 2- vinyl thiophene, stirs evenly, and continues to be cooled to 95 DEG C, benzene is added
52 parts of ethylene, be cooled to room temperature to get.Acid value 15mg/g.
Curing method: the peroxide of the 0.5wt% of composition weight is added into low temperature resistant unsaturated polyester resin compositions
Change cyclohexanone, stirs evenly, add the 0.01wt% cobalt iso-octoate of composition weight, form in a mold.
Comparative example 1
A kind of low temperature resistant unsaturated polyester resin compositions, in parts by weight, preparing raw material includes: maleic anhydride 49
Part, 120 parts of 1,9- nonanediol, 33.2 parts of M-phthalic acid, 26 parts of itaconic acid, 7.6 parts of 1,2- propylene glycol, 37.5 parts of triethylene glycol,
52 parts of styrene, 22 parts of 2- vinyl thiophene.
Preparation method: with High Purity Nitrogen exclude reaction kettle in air, be added 7.6 parts of 1,2-PD, 37.5 parts of triethylene glycol,
49 parts of maleic anhydride, 80 DEG C are warming up to, stirs 30min, is then added 33.2 parts of M-phthalic acid, then be warming up to 145 DEG C, is stirred
1h adds 120 parts of 1,9- nonanediol, is warming up to 210 DEG C, stirs 1h, adds 26 parts of itaconic acid, stirs 4h, is cooled to 160
DEG C, 22 parts of 2- vinyl thiophene are added, is stirred evenly, continues to be cooled to 95 DEG C, is added 52 parts of styrene, is cooled to room temperature, i.e.,
?.Acid value 36mg/g.
Curing method: the peroxide of the 0.5wt% of composition weight is added into low temperature resistant unsaturated polyester resin compositions
Change cyclohexanone, stirs evenly, add the 0.01wt% cobalt iso-octoate of composition weight, form in a mold.
Comparative example 2
A kind of low temperature resistant unsaturated polyester resin compositions, in parts by weight, preparing raw material includes: maleic anhydride 49
Part, 120 parts of 1,9- nonanediol, 33.2 parts of M-phthalic acid, 26 parts of itaconic acid, 7.6 parts of 1,2- propylene glycol, 37.5 parts of triethylene glycol,
34.4 parts of 3,4- thiophene dicarboxylic acid, 52 parts of styrene.
Preparation method: with High Purity Nitrogen exclude reaction kettle in air, be added 7.6 parts of 1,2-PD, 37.5 parts of triethylene glycol,
49 parts of maleic anhydride, 80 DEG C are warming up to, stirs 30min, is then added 33.2 parts of M-phthalic acid, then be warming up to 145 DEG C, is stirred
1h adds 120 parts of 1,9- nonanediol, is warming up to 210 DEG C, stirs 1h, adds 34.4 parts of 3,4- thiophene dicarboxylic acid and clothing health
26 parts of acid stirs 4h, is cooled to 95 DEG C, is added 52 parts of styrene, be cooled to room temperature to get.Acid value 42mg/g.
Curing method: the peroxide of the 0.5wt% of composition weight is added into low temperature resistant unsaturated polyester resin compositions
Change cyclohexanone, stirs evenly, add the 0.01wt% cobalt iso-octoate of composition weight, form in a mold.
Comparative example 3
A kind of low temperature resistant unsaturated polyester resin compositions, in parts by weight, preparing raw material includes: maleic anhydride 49
Part, 120 parts of 1,9- nonanediol, 33.2 parts of M-phthalic acid, 26 parts of itaconic acid, 7.6 parts of 1,2- propylene glycol, 37.5 parts of triethylene glycol,
52 parts of styrene.
Preparation method: with High Purity Nitrogen exclude reaction kettle in air, be added 7.6 parts of 1,2-PD, 37.5 parts of triethylene glycol,
49 parts of maleic anhydride, 80 DEG C are warming up to, stirs 30min, is then added 33.2 parts of M-phthalic acid, then be warming up to 145 DEG C, is stirred
1h adds 120 parts of 1,9- nonanediol, is warming up to 210 DEG C, stirs 1h, adds 26 parts of itaconic acid, stirs 4h, is cooled to 95
DEG C, be added 52 parts of styrene, be cooled to room temperature to get.Acid value 55mg/g.
Curing method: the peroxide of the 0.5wt% of composition weight is added into low temperature resistant unsaturated polyester resin compositions
Change cyclohexanone, stirs evenly, add the 0.01wt% cobalt iso-octoate of composition weight, form in a mold.
Test method
1. shock-testing
According to GB/T 11548, tested using XJL-300B tubing drop hammer impact testing machine.By embodiment 1-3 and right
Sample after ratio 1-3 solidifies pre-processes 2h when -15 DEG C and -20 DEG C；Drop hammer tup diameter 90mm, and quality of dropping hammer is 10kg,
Record shock height, unit mm.
2. shrinking percentage is tested
According to the shrinking percentage of the densimetry measurement embodiment 1-3 and comparative example 1-3 in ISO3521.
Test result is listed in the table below.
The above, preferable specific embodiment only of the invention, but scope of protection of the present invention is not limited thereto, appoints
What those familiar with the art the invention discloses in the range of, according to the technique and scheme of the present invention and inventive concept
It is subject to equivalent substitution or change, belongs to protection scope of the present invention.
Claims (10)
1. a kind of low temperature resistant unsaturated polyester resin compositions, which is characterized in that in parts by weight, preparing raw material includes: horse
Carry out 46-52 parts of acid anhydrides, 112-128 parts of straight chained alkyl glycol, 29-38 parts of M-phthalic acid, 22-29 parts of itaconic acid, 1,2- the third two
6-8 parts of alcohol, 33-42 parts of triethylene glycol, 30-38 parts of 3,4- thiophene dicarboxylic acid, 46-57 parts of styrene, 2- vinyl thiophene 19-25
Part.
2. low temperature resistant unsaturated polyester resin compositions as described in claim 1, which is characterized in that in parts by weight, system
Standby raw material includes: 49 parts of maleic anhydride, 120 parts of straight chained alkyl glycol, 33.2 parts of M-phthalic acid, 26 parts of itaconic acid, 1,2- third
7.6 parts of glycol, 37.5 parts of triethylene glycol, 34.4 parts of 3,4- thiophene dicarboxylic acid, 52 parts of styrene, 22 parts of 2- vinyl thiophene.
3. low temperature resistant unsaturated polyester resin compositions as described in claim 1, which is characterized in that the straight chained alkyl glycol
Contain 8-10 carbon atom.
4. low temperature resistant unsaturated polyester resin compositions as described in claim 1, which is characterized in that the straight chained alkyl glycol
For nonanediol.
5. low temperature resistant unsaturated polyester resin compositions as described in claim 1, which is characterized in that the styrene and 2- second
The molar ratio of alkenyl thiophene is 5:2.
6. low temperature resistant unsaturated polyester resin compositions as described in claim 1, which is characterized in that the 2- vinyl thiophene
Molar ratio with 3,4- thiophene dicarboxylic acid is 1:1.
7. the preparation method of low temperature resistant unsaturated polyester resin compositions as described in claim 1, which is characterized in that including such as
Lower step: the air in reaction kettle is excluded with High Purity Nitrogen, 1,2-PD 6-8 parts, 33-42 parts of triethylene glycol, maleic anhydride is added
46-52 parts, 80 DEG C are warming up to, stirs 30 min, is then added M-phthalic acid 29-38 parts, then be warming up to 145 DEG C, stirring 1
H adds 112-128 parts of straight chained alkyl glycol, is warming up to 210 DEG C, stirs 1 h, adds 30-38 parts of 3,4- thiophene dicarboxylic acid
With 22-29 parts of itaconic acid, stir 4 h, be cooled to 160 DEG C, be added 19-25 parts of 2- vinyl thiophene, stir evenly, continue to cool down
To 95 DEG C, be added styrene 46-57 parts, be cooled to room temperature to get.
8. the preparation method of low temperature resistant unsaturated polyester resin compositions as claimed in claim 7, which is characterized in that including such as
Lower step: the air in reaction kettle is excluded with High Purity Nitrogen, 7.6 parts of 1,2-PD, 37.5 parts of triethylene glycol, maleic anhydride 49 is added
Part, 80 DEG C are warming up to, 30 min are stirred, is then added 33.2 parts of M-phthalic acid, then be warming up to 145 DEG C, 1 h of stirring, then plus
Enter 120 parts of straight chained alkyl glycol, be warming up to 210 DEG C, stir 1 h, adds 34.4 parts of 3,4- thiophene dicarboxylic acid and itaconic acid 26
Part, 4 h are stirred, are cooled to 160 DEG C, 22 parts of 2- vinyl thiophene is added, stirs evenly, continues to be cooled to 95 DEG C, benzene second is added
52 parts of alkene, be cooled to room temperature to get.
9. the curing method of low temperature resistant unsaturated polyester resin compositions as described in claim 1, which is characterized in that resistance to low
The organic peroxide of 0.5 wt% is added in warm unsaturated polyester resin compositions, stirs evenly, it is different pungent to add 0.01wt%
Sour cobalt, forms in a mold.
10. low temperature resistant unsaturated polyester resin compositions as described in claim 1 are in auto industry, aircraft manufacturing, radar system
It makes, the application in ship, field of chemical equipment.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101137694A (en) * | 2005-01-18 | 2008-03-05 | 亚什兰许可和知识产权有限公司 | Low viscosity unsaturated polyester resin with reduced voc emission levels |
| CN101602849A (en) * | 2009-07-09 | 2009-12-16 | 湖南大学 | Dimer acid modified unsaturated polyester resin and synthetic method thereof |
| CN101735405A (en) * | 2009-12-29 | 2010-06-16 | 浙江天和树脂有限公司 | Imitation marble unsaturated polyester resin and preparation method thereof |
| CN106280196A (en) * | 2016-08-27 | 2017-01-04 | 安徽省新力复合材料有限公司 | A kind of heat resistant unsaturated polyester resin |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101137694A (en) * | 2005-01-18 | 2008-03-05 | 亚什兰许可和知识产权有限公司 | Low viscosity unsaturated polyester resin with reduced voc emission levels |
| CN101602849A (en) * | 2009-07-09 | 2009-12-16 | 湖南大学 | Dimer acid modified unsaturated polyester resin and synthetic method thereof |
| CN101735405A (en) * | 2009-12-29 | 2010-06-16 | 浙江天和树脂有限公司 | Imitation marble unsaturated polyester resin and preparation method thereof |
| CN106280196A (en) * | 2016-08-27 | 2017-01-04 | 安徽省新力复合材料有限公司 | A kind of heat resistant unsaturated polyester resin |
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